Waterproof varnish composition and process of making same.



UNITED srarss Pi OFFICE.

CHARLES A. HOLLENBECK, 01F ELIMHURST, AN D AARON C. HORN, OF NEW YORK, N. Y.

'WATERPROOF VARNISH COYMFOSITZGN AND PROCESS OF MAKING- SAME.

No Drawing.

T 0 all whom it may concern:

Be it known that we, Ci-rAnLns A. Hot.- LENBECK and AARON C. HORN, citizens of the United States, and residents, respectively, of Elmhurst; in the county of Queens and State of New York, and New York. in the county of New York and State of New York, have invented certain new and use ful Improvements in Waterproof Varnish Compositions and Processes of Making v Same, of which the following is a specification.

This invention relates to a process of making a varnish composition and to the product of such process and relates in particular to the production oi varnishes having certain novel properties, as will be more fully hereinafter described.

According to the present methods of making oil varnishes, it is customary to melt the resins employed and heat them to a high temperature. until they lose 20 to 25% in weight, by the distillation of more volatile components and by the destructive decomposition or destructive distillation which involves the breaking down oi some of the compounds of hydrogen, carbon and oxygen, of a relatively low degree of stability to yield a cracked product of a high degree of hardness which in distinction to the original resin is comparatively soluble in oils and varnish thinners such as turpentine and benzin. Such cracked resins, although prepared from the harder varieties of copal give difliculty in incorporating with siccative oils to produce a varnish composition having the desired degree of waterproofing qualities. The dried coating of an ordinary varnish is more or less porous and by some this defect is ascribed to the result of abpermeable to a greater or less degree. The bubbles of gas liberated are of course microscopic in size but moisture will eventually find its way into these spaces and by the action of the weather such places of entry become enlarged and ultimately I orm fissures, so with aging and weathering the varnish coat becomes marred in appearance and is eventually destroyed. Consequently,

it is of great importance for permanency of a varnish coating to produce a film which when dry is substantially impermeable to Specification of Letters Patent.

Patented July 11, 1916.

moisture and by the-usual methods, as indicated, there is a considerable degree of dilliculty in producing a film having these very desirable qualities. 1

By the present invention as will be hereinafter detailed in. a manner such that those skilled in theart may readily practise same, a varnish composition is derived which possesses waterproofing qualities of a very pronounced character and which furthermore in the preferred form or embodiment of'the invention has other desirable and novel properties, including a marked resistance to chemical reagents such as ammonia and similar compounds and which is characterized-by a relatively high resistance to solvents such as alcohol, es-

A furtherfeature of the present composition is that it flows freely under the brush and yields a fine smooth finish which dries quickly and'becomes when dry very hard, while at the same time maintaining a degree of flexibility or elasticity which is unusual in view of the hurddurable character of the film.

Another feature of the product in its preferred form is the absence of anysubstantial skin or film formation when the varnish is allowed to stand in closed containers. Many varnishes and especiallythose prepared with Chinese wood oi1,-when ;pre served in containers such as the ordinary tin cans used in packaging varnish, on being allowed to stand awayfromthe air, except for that'which may be present in the dead space of the can exhibit avery objectionable defect, namely that of forming a skin or pellicle over the surface, which in some cases is so tough that it can bebroke'n only with difficulty and which of course represents a loss of varnish material to the consumer. By the present invention it becomes ossible to ore are a varnish which the can of material has been opened and quantities drawn therefrom from time to time so that additional air enters the container, there is ordinarily no formation of a skin of any objectionable thickness. In fact with the present product we have noticed that a t'tcr a can containing the material has been opened several times, in case a film does form it is of such a character as to be easily broken by tilting the container and in consequence the loss through drying of the varnish therein is not material in any case. In spite of the fact that there is no such undesiral'ile pellicle formation in th container, the film which forms on exposure to the air is of a hard, durable, elastic uature-propcrties which would not be expected in view of the lack of formation of a tough skin in the container. In a preferred cmbodilmalt of this invention the-product derived possesses these properties in a marked degree, which feature constitutes another element of novelty of the present composition.

According to the present invention various siccative or drying oils, or even semi' drying oils. including perilla. Chinese wood oil. tomato seed. candle nut. corn. cotton se'ed. rape seed. fish. whale, castor oil and the like maybe used. Preferably however, siccative oils are employed and in particular, we prefer an oil of the nature of Chinese wood oil. capable of being polymerized with gclatinization by heating. Instead of treat ing such oil or oils with oxygen by pro-' tracted boilinwe preferably saturate the oil to a considerable extent with sulfur, which combines with the oil readily when heated therewith. forming what appear to be polymerized sulfuretcd complexes. consisting of a chain of the (hincse wood oil molecules connccted by atoms of sulfur at the place of double bonding. such chain of molecules being of greater and greater length, according to the viscosity and degree of resistance or imlwnetrability to moisture. The peculiar properties of Chinese wood oil. for example the phenomena of gelatiuization by simple heating caused by the presence in predominating amount of oleoinargaric glycerid apparently renders this oil especially susceptible to the sulfuring process. According to the latter process the oil is heated with a quantity of sulfur. relatively small in amount, but sullicientto bring about a certain degree of saturation by such interlocking of oil molecules during the chaining action of the sulfur to form sulfureted composite polymers,

It is desirable to approximate or somewhat exceed the. normal temperature of heat polymerization when forming an oil basis when heating a hcat-polymerizaldo drying oil with sulfurin order to secure the most satisfactory results and toobtain a product tained by incorporating with the oil, a con siderable quantity of hard copal resin, or'

what is known in the varnish makers terminology as hard gum. In order to obtain a product of the highest etliciency,- the resin is preferably subjected to a re-melting 0r re-running treatment, which gives the ma.- terial properties of unusual value for the present purpose. If a varnish resin or hard gum is simply heated to bring about cracking to such an extent as to yield a soluble product the once run resin ordinarily is apparently not capable of producing that peculiar colloidal condition which prevents water penetration -to a sutliciently effective extent in the case of-dried films of the resulting varnish. (In the other'hand, if the resin is first melted and run to crack to a condition of solubility and the operation completed at a lower temperature. or preferably if the material is allowed to become cold and solidified andthe solidified run resin is heated above the melting point, preferably at a temperature somewhat lower than the original cracking temperature there apparently occur a series of complex chemical changes in the resin by virtue of this duplex melting process. which causes a hardening and polymerization or other intricate change enabling the resin to so intermingle with the oil. that a remarkably durable. tough varnish product is secured. Just whatthe changes are that take place in the heating of the resin under these conditions is dillicult to state but in part they may be a partial breaking down of the resin acids to produce anhydrids which subzwquently polymerize during the second heating operation.

A formula which will illustrate the invention along specific lines is the following; a copal gum. or more properlyspeaking, u copal resin is melted and heated to 610630 F" until moisture, essential oils and other volatile materials are driven off and the oil suitably cracked, by which operation the resin loses from 15 to 30% of its weight. IV hen this stage is reached the resin is allowed to cool for about 24 hours in order to allow any reaction which may take place under these conditions, to progress to a sulfieient degree ofcompletion. The run resin is then melted at a somewhat lower temperature, usually between 450 and 500 F. During the second melting some condense: tion of the resin molecules apparently oeeurs. In the meantime a sulfured oil is prepared by heating Chinese woodoil with flowers of sulfur, usually 15 to 25 pounds of mo -ma sulfur being used to 5 gallons of the oil and the resin, thus giving both sul'i'ured oil and a sulil ured resin. Also in some cases the final product may contain l re-c suliur, which is not objectionable, but is even useful for some purposeswhile in other applications the presence of any material amount of tree sulfur would be undesirable and the opcrzu tion should he conducted carefully to secure as near as possible a complete combination of the sulfur with the oil. The proportion of the resin to the oil varies, depending on Whether it is desired to produce a long oil varnish. for exterior worlr, or a. short oil varnish" for interior application, A suitable drier is also incorporated while for this purpose, while other driers may be employed, we find cobalt linoleate to be the most efficient in connection ch sulfur-ed oil and we preferably employ this or similar oil-soluble cobalt body, or a compound drier containing cobalt and other metallic drier according to circumstances. When the run resin and the sulfured wood oil have been mixed and are suitably combined or incorporated by heating, the product is cooled sullicientlyand suitably thinned With any desirable varnish thinner, such as turpentine, benzin. or varnish naphtha, coal tar naphtha and the like. A specific formula traversing the foregoing consists of 100 pounds of copal resin, 18 gallons of sulfured wood oil, 1 pound of cobalt linolcate and 40 gallons of turpentine.

As indicated above the foregoing formula is sul'imittcd as illustrative modifications or deviations therefrom may be made according to the character of the varnish required for the particular application in hand; While it desirable to use only the hardest varieties of copal, including kauri gum and also (loose or pontianak for the production of the highest grade of waterproof varnish, it is possible to prepare somewhat lower grade products, which can be rubbed, by the use of small or modcrato amounts of colophony, which under these conditions does not need to be hardened by a lime or similar treatment for use in this manner. Simila *ly, a cheaper but durable varnish may be made by substituting, the

bard resin largely or entirely hy colophony. In the latter case the material dries to a and various hard tough varnish which when some hard rosin is present is so hard that the coating may be eventually rubbed with pumice and water, or with oil. arnishes may be prepared whichfiow readily under thebrush, due to their fine colloidal character, and will dry dust-free in 5 hours and will be. dry'in 48 hours, while in 60-72 hours these coatings may be rubbed. In place 0t colophony, its esters with glycerin andthelilcc may be employed.

Besides the process herein set forth for making a waterproof varnish, involving in its specific aspects of cracking a resin, cooling to solii'li'l'y, rcuielting the solidified product, incorpimating with a sulfured drying'oil and a cobalt dric' and thinning the composite to the consistency of varnish, we also embrace in the present invention the product of the process broadly stated or as specifically set forth above, including a colloidal varnish, comprising a reversible resinous colloid, a drier and a polymerized sulfureted siccative oil (301I1]')l0;( of high molecular weight; also the product comprising remelted resin as a reversible colloid and we further embrace a varnish capable of drying to a tough.impervious film on expo sure which is substantially or essentially free from pellicle-iormation in a closed containor.

The several features of our invention are forth concisely in the appended claims.

What we claim is l. The process of making a Waterproof varnish which comprises melting a hard varnish resin and heating to render same soluble in a. varnish vehicle, cooling to solidify, remelting the solidified product, incorporating with a suli'ured drying oil and a drier, and thinning; the composite to the consistency oi varnish. v

2. The process of making a Waterproof. varnish which comprises melting ahard var nish resin and heating to render same s0lu-, ble a varnish vehicle, cooling to solidify, rcmelting the solidified product, incorporate ing with sulfured Chinese wood oil anda 1 drier, and thinning the composite to the consistency of varnish.

3. process of making varnish which comprises melting a hard. varnish and heating: to render same soluble in a varnish vehicle. cooling, to solidify, remeltinp; the solidified product, incorporating with a. sulturcd dryiugr oil and a drier, and thinning the composite to the consistency of varnish.

4. In a process of making a waterproof varnish the step which comprises rcmelting run resin and incorporating, the remelted product with a sullured drying oil.

5. A varnish product consisting of a light colored siccative composition of the consistency of varnish comprising a remelted,

fured Chinese Wood oil which is substantially or essentially free from pellicle-formation in a closed container.

9. A Varnish having substantially the properties of a spar varnish but with enhanced Waterproofing qualities and containing remelted resin and a sulfurcd Chinese Wood oil soluble in turpentine.

Signed at Long Island city in the county of Queens and State of New York this 29th day of December A. D. 1914. 1 s

CHARLES A. HOLLENBECK. AARON C. HORN. Witnesses:

J. F. HAMMOND, JNo. H. SCHUBERT. 

